Catalyst for the polymerization of olefins

ABSTRACT

A catalyst for the polymerization of olefins made from or containing (a) a solid catalyst component containing Mg, Ti and optionally an internal electron donor compound (ID), (b) an aluminum alky compound, and (c) an external electron donor (ED) selected from non-aromatic diazo compounds.

FIELD OF THE INVENTION

In general, the present disclosure relates to the field of chemistry.More specifically, the present disclosure relates to polymer chemistry.In particular, the present disclosure relates to Ziegler-Natta catalystsfor the polymerization of olefins.

BACKGROUND OF THE INVENTION

In some instances, catalyst components are used for the stereospecificpolymerization of olefins. In some instances, Ziegler-Natta catalystsmade from or containing a solid catalyst component, constituted by amagnesium dihalide on which are supported a titanium compound and,optionally, an internal electron donor compound, are used with anAl-alkyl compound, for polymerizing propylene.

In the preparation of isotactic polypropylene, an external donorincreases catalyst stereospecificity.

In some instances, and for ethylene polymerization, ZN catalysts containethers as external donors to impart specific properties to thecatalysts.

SUMMARY OF THE INVENTION

In a general embodiment, the present disclosure provides nitrogencontaining non-aromatic donors for use as external donors for ethyleneand propylene polymerization.

In a general embodiment, the present disclosure provides a catalyst forthe polymerization of olefins made from or containing (a) a solidcatalyst component containing Mg, Ti and optionally an internal electrondonor compound (ID), (b) an aluminum alky compound, and (c) an externalelectron donor (ED) of formula (I)

wherein the R¹ to R³ groups, equal to, or different from, each other,are selected from hydrogen or C₁-C₁₅ hydrocarbon groups, R group isselected from hydrogen, C₁-C₁₅ hydrocarbon groups, and —NR₂ groups,wherein R groups have the same meaning as R¹ to R³ groups. In someembodiments, independently, the couples formed by R¹-R⁴ and R²-R³ arejoined together to form non-aromatic cyclic structures.

DETAILED DESCRIPTION OF THE INVENTION

In some embodiments, the solid catalyst component (a) contains at leastone internal electron donor compound (ID) being a molecule containing atleast one functional group selected from the group consisting of esters,ethers, ketones, carbamates, carbonates, amines, amides, nitriles,alkoxysilanes, and mixtures thereof.

In some embodiments, the ID compound is monofunctional ormultifunctional. As used herein, the phrase “monofunctional ormultifunctional” refers to a molecule containing one or more functionalgroups. In some embodiments, the multifunctional molecules havefunctional group belonging to the same or different class.

In some embodiments, and for the polymerization of propylene, the IDcontains two or more functional groups selected from the groupconsisting of esters, ethers, ketones, carbamates, and carbonates.

In some embodiments, the IDs are selected from the group consisting ofIDs containing two functional groups (bidentate). In some embodiments,the functional groups for bidentate IDs are selected from the groupconsisting of alkyl and aryl esters of mono or polycarboxylic acids. Insome embodiments, the esters are selected from esters of benzoic,phthalic, malonic, and succinic acid. In some embodiments, the estersare selected from the group consisting of n-butylphthalate,di-isobutylphthalate, di-n-octylphthalate, diethyl2,2-diisopropylsuccinate, diethyl 2,2-dicyclohexyl-succinate,ethyl-benzoate, p-ethoxy ethyl-benzoate, and diethyl3,3-di-n-propylglutarate.

In some embodiments, the bidentate IDs are 1,3 diethers of formula (II):

where R^(I) and R^(II) are the same or different and are hydrogen orlinear or branched C₁-C₁₈ hydrocarbon groups; R^(III) groups, equal ordifferent from each other, are hydrogen or C₁-C₁₈ hydrocarbon groups;R^(IV) groups equal or different from each other, have the same meaningof R^(III) except that R^(IV) groups cannot be hydrogen. In someembodiments, R^(I) or R^(II) has constituents of cyclic structures. Insome embodiments, each of R^(I) to R^(IV) groups contains heteroatomsselected from halogens, N, O, S and Si.

In some embodiments, R^(IV) is a 1-6 carbon atom alkyl radical,alternatively a methyl. In some embodiments, the R^(III) radicals arehydrogen. In some embodiments, R^(I) and R^(II) are joined to formcyclic structure as described in European Patent Publication No.EP728769A1.

In some embodiments, mixtures of 1,3-diethers are used in the solidcatalyst component. In some embodiments, the internal electron donor isselected from the group of mixtures of esters of aliphatic dicarboxylicacids with the 1,3-diethers of formula (II). In some embodiments, theesters of aliphatic dicarboxylic acids are selected from the groupconsisting of malonates, succinates, and glutarates. In someembodiments, the 1,3-diethers of formula (II) are as described in PatentCooperation Treaty Publication No. WO2012/139897.

In some embodiments, the bidentate IDs are dicarbamates having formula(III):

where R⁵ and R⁶, independently, are selected from hydrogen and C₁-C₁₅hydrocarbon groups, optionally contain a heteroatom selected fromhalogen, P, S, N, O, and Si and A is a bivalent bridging group. In someembodiments, R⁵ and R⁶ are fused together to form one or more cycles.

In some embodiments, the dicarbamate structures of formula (III) are asdescribed in Patent Cooperation Treaty Publication No. WO2014048861,incorporated herein by reference.

In some embodiments, and for the polymerization of ethylene, the IDs aremonofunctional IDs. In some embodiments, the monofunctional IDs areselected from the group consisting of C₁-C₈ alkyl esters of aliphaticmono carboxylic acids. In some embodiments, the C₁-C₈ alkyl esters ofaliphatic mono carboxylic acids are selected from the group consistingof ethylacetate, methyl formiate, ethylformiate, methylacetate,propylacetate, i-propylacetate, n-butylacetate, and i-butylacetate. Insome embodiments, the C₁-C₈ alkyl ester of an aliphatic mono carboxylicacid is ethylactetate.

In some embodiments, the monofunctional IDs are selected from the groupconsisting of C₂-C₂₀ aliphatic ethers, alternatively cyclic ethers,alternatively having 3-5 carbon atoms. In some embodiments, themonofunctional IDs are selected from the group consisting oftetrahydrofuran and dioxane. In some embodiments, the monofunctional IDsare selected from the group consisting of linear C₂-C₂₀ aliphaticethers. In some embodiments, the monofunctional IDs are linear C₂-C₂₀aliphatic ethers selected from the group consisting of dimethyl ether,diethyl ether and isoamyl ether.

In some embodiments, two or more monofunctional IDs are present in thesolid catalyst component (a). In some embodiments, a first ID isselected from aliphatic ethers and a second ID is selected fromaliphatic acid esters. In some embodiments, the aliphatic ether istetrahydrofuran, and the aliphatic acid ester is ethyl acetate. In someembodiments, the molar ratio between the aliphatic acid ester and theether in the final solid catalyst component ranges from 0.2:1 to 16:1,alternatively from 0.5:1 to 10:1.

In some embodiments, the amount of magnesium present in the solidcatalyst component ranges from 5 to 25% wt, alternatively from 13 to 21%wt, based upon the total weight of the solid catalyst component.

In some embodiments, the amount of chlorine present in the solidcatalyst component is greater than 30% wt, alternatively greater than40%, alternatively ranging from 40 to 80% wt., with respect to the totalweight of the catalyst component

In some embodiments, the amount of titanium atoms present in the solidcatalyst component is greater than 1%, alternatively greater than 1.5%wt, alternatively ranges from 1.5 to 6% wt, with respect to the totalweight of the solid catalyst component.

In some embodiments, the ID is present in the solid catalyst componentin an amount ranging from 1 to 30% by weight, alternatively from 3 to20% by weight, with respect to the total weight of the solid catalystcomponent.

In some embodiments, the molar ratio of the ID with respect to the Tiatoms ranges from 0.2:1 to 15:1, alternatively from 0.5:1 to 13:1.

In some embodiments, and in the ED of formula (I), R¹ is selected fromC₁-C₁₅ hydrocarbon groups.

In some embodiments, and in the external donor ED of formula (I), R¹ andR² are selected from C₁-C₁₀, alternatively C₁-C₅, alkyl groups; R³ isselected from hydrogen or C₁-C₅ alkyl groups, and R⁴ is selected from—NR₂ groups. In some embodiments, R is selected from hydrogen or C₁-C₅alkyl groups. In some embodiments, the external donor (ED) is selectedfrom the group consisting of 1,1-dipropylguanidine,1-ethyl-1-propylguanidine, 1-methyl-1-propylguanidine,1-butyl-1-propylguanidine, 1-ethyl-1-methylguanidine,1,1-dimethylguanidine, 1-butyl-1-methylguanidine, 1,1-diethylguanidine,1-butyl-1-ethylguanidine, 1,1-dibutylguanidine,1-butyl-3,3-dimethyl-1-propylguanidine,1-butyl-1-ethyl-3,3-dimethylguanidine, 1-butyl-1,3,3-trimethylguanidine,1,1-dibutyl-3,3-dimethylguanidine,1-butyl-3,3-diethyl-1-propylguanidine, 1-butyl-1,3,3-triethylguanidine,1-butyl-3,3-diethyl-1-methylguanidine, 1,1-dibutyl-3,3-diethylguanidine,1-ethyl-3,3-dimethyl-1-propylguanidine,1,1,3-triethyl-3-propylguanidine, 1,1-diethyl-3,3-dimethylguanidine,1-ethyl-1,3,3-trimethylguanidine, 1,1,3,3-tetraethylguanidine,1,1,3,3-tetramethylguanidine, 1,1,3-triethyl-3-methylguanidine,1,1,3-trimethyl-3-propylguanidine,1,1-diethyl-3-methyl-3-propylguanidine,1,1-diethyl-3,3-dimethylguanidine, 1,1-dimethyl-3,3-diproylguanidine,and 1,1-diethyl-3,3-dipropylguanidine]. In some embodiments, theexternal donor (ED) is 1,1,3,3-tetramethyl guanidine (TMG).

In some embodiments, the ED of formula (I) is coupled with solidcatalyst component (a) made from or containing a difunctional ID.

In some embodiment, and in the external donor ED of formula (I), thecouples of R¹-R⁴ and R²-R³ are joined together to form non-aromatic ringstructures. In some embodiments, the couples of R¹-R⁴ and R²-R³ arejoined to form ring structures. In some embodiments, the rings are madeof five or more members. In some embodiments, the couple R¹-R⁴ forms a5-7 members saturated ring structure, and the couple R²-R³ forms asix-member unsaturated ring, having a C═N double bond. In view of thebackbone of the ED of formula (I), when the couples of R¹-R⁴ and R²-R³are joined together to form non-aromatic cyclic structures, EDs havingfused heterocyclic rings are obtained. In some embodiments, the ED offormula (I) is selected from the group consisting of2,5,6,7-tetrahydro-3H-pyrrolo[1,2-a]imidazole,2,3,5,6,7,8-hexahydroimidazo[1,2-a]pyridine,2,5,6,7,8,9-hexahydro-3H-imidazo[1,2-a]azepine,2,3,4,6,7,8,9,10-octahydropyrimido[1,2-α]azepine,1.8-diazabicyclo[5.4.0]undec-7-ene,3,4,6,7,8,9-hexahydro-2H-pyrido[1,2-α]pyrimidine,1,5-diazabicyclo[4.3.0]non-5-ene], and2,3,4,6,7,8-hexahydropyrrolo[1,2-α]pyrimidine. In some embodiments, theED of formula (I) is selected from the group consisting of1.8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN).

In some embodiments, the ED of formula (I) is coupled with solidcatalyst component (a) further made from or containing a monofunctionalID.

In some embodiments, the solid catalyst components (a) are made from orcontaining a titanium compound, having at least a Ti-halogen bond. Insome embodiments, the solid catalyst components (a) are made from orcontaining a titanium compound, having at least a Ti-halogen bondsupported on a Mg halide and an ID compound. In some embodiments, themagnesium halide is MgCl₂ in active form. In some embodiments, MgCl₂ inactive form is a support for Ziegler-Natta catalysts as described inU.S. Pat. Nos. 4,298,718 and 4,495,338.

In some embodiments, the titanium compounds are selected from the groupconsisting of TiCl₄ and TiCl₃. In some embodiments, the titaniumcompounds are selected from the group consisting of Ti-haloalcoholatesof formula Ti(OR⁶)_(m-y)X_(y), wherein m is the valence of titanium, yis a number between 1 and m−1, X is halogen, and R⁶ is a hydrocarbonradical having from 1 to 10 carbon atoms.

In some embodiments, the solid catalyst component is prepared by areaction between magnesium alcoholates or chloroalcoholates and anexcess of TiCl₄, in the presence of the electron donor compounds, at atemperature of about 80 to 120° C. In some embodiments, thechloroalcoholates are prepared as described in U.S. Pat. No. 4,220,554.

In some embodiments, the solid catalyst component is prepared byreacting a titanium compound of formula Ti(OR⁷)_(m-y)X_(y), wherein m isthe valence of titanium and y is a number between 1 and m, with amagnesium chloride deriving from an adduct of formula MgCl₂.pR⁸OH,wherein p is a number between 0.1 and 6, alternatively from 2 to 3.5,and R⁸ is a hydrocarbon radical having 1-18 carbon atoms. In someembodiments, the titanium compound of formula Ti(OR⁷)_(m-y)X_(y) isTiCl₄. In some embodiments, the adduct is prepared in spherical form bymixing alcohol and magnesium chloride in the presence of an inerthydrocarbon immiscible with the adduct, operating under stirringconditions at the melting temperature of the adduct (100-130° C.). Then,the emulsion is quickly quenched, thereby causing the solidification ofthe adduct in form of spherical particles. In some embodiments, theprocedure for the preparation of the spherical adducts are as describedin U.S. Pat. Nos. 4,399,054 and 4,469,648. In some embodiments, theadduct is directly reacted with Ti compound or subjected to thermalcontrolled dealcoholation (80-130° C.), thereby obtaining an adductwherein the number of moles of alcohol is lower than 3, alternativelybetween 0.1 and 2.5. In some embodiments, the reaction with the Ticompound is carried out by suspending the adduct (dealcoholated or assuch) in cold TiCl₄. In some embodiments, cold TiCl₄ is at about 0° C.In some embodiments, the mixture is heated up to 80-130° C. andmaintained at this temperature for 0.5-2 hours. In some embodiments, thetreatment with TiCl₄ is carried out one or more times. In someembodiments, the electron donor compound is added during the treatmentwith TiCl₄. In some embodiments, the preparation of catalyst componentsin spherical form is as European Patent Applications Nos. EP-A-395083,EP-A-553805, EP-A-553806, and EPA601525 and Patent Cooperation TreatyPublication No. WO98/44009.

In some embodiments, in a first step (i) carried out at a temperatureranging from 0 to 150° C., a Mg based compound is reacted with a Ticompound, having at least a Ti—Cl bond, in an amount such that the Ti/Mgmolar ratio is greater than 3, thereby generating an intermediate solidcatalyst component containing Mg and Ti In some embodiments, the Mgbased compound is from an adduct of formula MgCl₂.pR⁸OH. In someembodiments, in a step (ii), the intermediate solid catalyst componentis contacted with an electron donor compound ID.

In some embodiments, the solid catalyst components show a surface area(by B.E.T. method) between 20 and 500 m²/g, alternatively between 50 and400 m²/g, and a total porosity (by B.E.T. method) higher than 0.2 cm³/g,alternatively between 0.2 and 0.6 cm³/g. In some embodiments, theporosity (Hg method) due to pores with radius up to 10.000 Å ranges from0.15 to 1.5 cm³/g, alternatively from 0.25 to 1 cm³/g.

In some embodiments, the solid catalyst component has an averageparticle size ranging from 5 to 120 μm, alternatively from 10 to 100 μm.

In some embodiments, the alkyl-Al compound (b) is a trialkyl aluminumcompound. In some embodiments, the trialkyl aluminum compounds areselected from the group consisting of triethylaluminum,triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, andtri-n-octylaluminum. In some embodiments, the alkyl-Al compound (b) isselected from alkylaluminum halides, alkylaluminum hydrides,alkylaluminum sesquichlorides, and mixtures with trialkylaluminums. Insome embodiments, the alkylaluminum sesquichlorides is AlEt₂Cl orAl₂Et₃C₃.

In some embodiments, the ED electron donor compound of formula (I) isused in such an amount to give a molar ratio between the organoaluminumcompound and the ED of from 0.1 to 500, alternatively from 1 to 300,alternatively from 3 to 100.

In some embodiments, the present disclosure provides a process for thehomopolymerization or copolymerization of olefins CH₂═CHR, wherein R ishydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out inthe presence of the catalyst.

In some embodiments, the polymerization process is carried out withslurry polymerization using as diluent an inert hydrocarbon solvent orbulk polymerization using the liquid monomer as a reaction medium. Insome embodiments, the liquid monomer is propylene. In some embodiments,the polymerization process is carried out in gas-phase operating in oneor more fluidized or mechanically agitated bed reactors.

In some embodiments, the polymerization is carried out at temperature offrom 20 to 120° C., alternatively from 40 to 80° C. In some embodiments,the polymerization is carried out in gas-phase with the operatingpressure between 0.5 and 5 MPa, alternatively between 1 and 4 MPa. Insome embodiments, the is carried out bulk polymerization with theoperating pressure ranges between 1 and 8 MPa, alternatively between 1.5and 5 MPa.

The following examples are given to further illustrate the disclosurewithout being intended as limiting the disclosure.

Characterizations Determination of X.I.

2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomedflask provided with a cooler and a reflux condenser and kept undernitrogen. The mixture was heated to 135° C. and kept under stirring forabout 60 minutes. The final solution was cooled to 25° C. undercontinuous stirring. The insoluble polymer was then filtered. Thefiltrate was then evaporated in a nitrogen flow at 140° C. to reach aconstant weight. The content of the xylene-soluble fraction is expressedas a percentage of the original 2.5 grams and then, by difference, theX.I. %.

Determination of Donors.

The content of electron donor was determined via gas-chromatography. Thesolid component was dissolved in acidic water. The solution wasextracted with ethyl acetate, an internal standard was added, and asample of the organic phase was analyzed in a gas chromatograph, therebydetermining the amount of donor present at the starting catalystcompound.

Melt Flow Rate (MFR)

The melt flow rate MIL of the polymer was determined according to ISO1133 (230° C., 2.16 Kg)

Determination of Melt Index (MIE, MIF, MIP)

The melt indices were measured at 190° C. according to ASTM D-1238,condition “E” (load of 2.16 kg), “P” (load of 5.0 kg) and “F” (load of21.6 kg).

The ratio between MIF and MIE is indicated as F/E, while the ratiobetween MIF and MIP is indicated as F/P.

Determination of Comonomer Content

1-Butene was determined via ¹³C NMR analysis.

¹³C NMR spectra were acquired on a Bruker AV-600 spectrometer equippedwith cryo-probe, operating at 150.91 MHz in the Fourier transform modeat 120° C.

The peak of the Sδδ carbon (nomenclature according to C. J. Carman, R.A. Harrington and C. E. Wilkes, Macromolecules, 10, 3, 536 (1977)) wasused as internal reference at 29.90 ppm. The samples were dissolved in1,1,2,2-tetrachloroethane-d2 at 120° C. with an 8% wt/v concentration.Each spectrum was acquired with a 90° pulse, 15 seconds of delay betweenpulses and CPD to remove ¹H-¹³C coupling. About 512 transients werestored in 32K data points using a spectral window of 9000 Hz.

Assignments of the spectra were made according to J. C. Randal,Macromol. Chem Phys., C29, 201 (1989).

Triad distribution and composition were made starting from relationsbetween peaks and triads described by Kakugo et al. modified to consideroverlaps of signals in the spectra.

Triads

BBB=100Tββ/S

BBE=100Tβδ/S

EBE=100 2B2(EBE)/S

BEB=100Sββ/S

BEE=100Sαδ/S

EEE=100(0.25Sγδ+0.5Sδδ)/S

Molar Composition

B=BBB+BBE+EBE

E=EEE+BEE+BEB

Determination of Fraction Soluble in Xylene

2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomedflask equipped with a cooler and a reflux condenser and kept undernitrogen. The resulting mixture was heated to 135° C. and kept understirring for about 60 minutes. The final solution was cooled to 25° C.under continuous stirring. The insoluble polymer was then filtered. Thefiltrate was then evaporated in a nitrogen flow at 140° C. to reach aconstant weight. The content of the xylene-soluble fraction is expressedas a percentage of the original 2.5 grams.

Determination of Effective Density

Effective density: ASTM-D 1505-10 but referred to MI″E″ 1 g/10′ ascorrected by the following equation: density(MIE=1)=density(measured)−0.0024 ln(MI E).

EXAMPLES General Procedure for the Polymerization of Propylene

A 4-liter steel autoclave equipped with a stirrer, pressure gauge,thermometer, catalyst feeding system, monomer feeding lines, andthermostatic jacket, was purged with nitrogen flow at 70° C. for onehour. Then, at 30° C. under propylene flow, were charged in sequencewith 75 mL of anhydrous hexane, 0.76 g of AlEt₃, the external electrondonor, thereby providing an Al/Donor molar ratio of 20, and 0.006÷0.010g of solid catalyst component. The autoclave was closed. Then, 2.0 NL ofhydrogen were added. Then, under stirring, 1.2 kg of liquid propylenewere fed. The temperature was raised to 70° C. in five minutes. Thepolymerization was carried out at this temperature for two hours. At theend of the polymerization, the unreacted propylene was removed. Thepolymer was recovered and dried at 70° C. under vacuum for three hours.Then, the polymer was weighed and fractionated with o-xylene, therebydetermining the amount of the xylene insoluble (X.I.) fraction. Polymercharacteristics are reported in Table 3.

General Procedure for the LLDPE Polymerization Test in Slurry

A 4.5-liter stainless-steel autoclave equipped with a magnetic stirrer,temperature, pressure indicator, and feeding line for ethylene, propane,1-butene, and hydrogen, and a steel vial for the injection of thecatalyst, was purified by fluxing pure nitrogen at 70° C. for 60minutes. The autoclave was then washed with propane, heated to 75° C.,and finally loaded with 800 grams of propane, 1-butene (in the amountvariable between 160 g and 200 g), ethylene (7.0 bar, partial pressure),and hydrogen (1.5 bar, partial pressure). In a separate 100 cm³ roundbottom glass flask, 50 cm³ of anhydrous hexane, a cocatalyst mixturesolution made from or containing triethyl aluminum/diethyl aluminumchloride (that is, TEA/DEAC 2/1 weight ratio (8.5 mmol of aluminum)),tetrahydrofuran or a compound of formula (I) as external donor (Al/EDmolar ratio as indicated in Table 2), and 0.010÷0.020 grams of the solidcatalyst component were subsequently introduced. The contents of theround bottom flask were mixed and stirred at room temperature for 10minutes and then introduced to the reactor through the steel vial byusing nitrogen overpressure. Under continuous stirring, the totalpressure was maintained constant at 75° C., thereby absorbing 150 g ofethylene, for a maximum time of 2 h by continuous ethylene feeding intothe system. At the end of the polymerization, the reactor wasdepressurized. The temperature was reduced to 30° C. The recoveredpolymer was dried at 70° C. under a nitrogen flow and weighed. Polymercharacteristics are reported in Table 2.

General Procedure for the HDPE Polymerization Test PolymerizationsConditions for Catalyst A

A 4.5-liter stainless-steel autoclave equipped with a magnetic stirrer,temperature and pressure indicator, and a feeding line for hexane,ethylene, and hydrogen, was purified by fluxing pure nitrogen at 70° C.for 60 minutes. Then, a solution of 1550 cm³ of hexane containing 0.1 gof triethyl aluminum (TEA) was introduced at a temperature of 25° C.under nitrogen flow to the autoclave. In a separate 100 cm³ round bottomglass flask, 50 cm³ of anhydrous hexane, 0.4 g of triethyl aluminum(TEA), 0.025 grams of the solid catalyst component, and the amount ofexternal donor reported in Table 1 were introduced. The components weremixed, aged 10 minutes at room temperature, and introduced undernitrogen flow into the reactor. The autoclave was closed. Thetemperature was raised to 75° C. Hydrogen (4 bars partial pressure) andethylene (7.0 bars partial pressure) were added. Under continuousstirring, the total pressure was maintained at 75° C. for 120 minutes byfeeding ethylene. At the end of the polymerization, the reactor wasdepressurized. The temperature was reduced to 30° C. The recoveredpolymer was dried at 40° C. under vacuum and analyzed. Polymercharacteristics are reported in Table 1.

Polymerizations Conditions for Catalyst B

The procedure for catalyst A was repeated, except tri-isobutyl aluminum(TIBA) was used instead of triethyl aluminum (TEA). 0.35 g of TIBA wentinto autoclave and 0.15 g went into the precontact solution.Furthermore, the polymerization time was 3 h, instead of 2 h Polymercharacteristics are reported in Table 1.

General Procedure for the Preparation of the Solid Catalyst Componentfor the LLDPE Polymerization Test in Slurry

An initial amount of microspheroidal MgCl₂.2.8C₂H₅OH was preparedaccording to the method described in Example 2 of Patent CooperationTreaty Publication No. WO98/44009. The resulting microspheroidalMgCl₂-EtOH adduct was subjected to a thermal treatment under nitrogenstream over a temperature range of 50-150° C., thereby reducing thealcohol content. A solid support material containing 28.5% wt of EtOH,having an average particle size of 23 μm, was obtained.

Into a 750 mL four-necked round flask, purged with nitrogen, 500 mL ofTiCl₄ were introduced at 0° C. Then, at the same temperature, 20 gramsof microspheroidal adduct were added under stirring. The temperature wasraised to 130° C. and maintained at that temperature for 1 hours. Then,the stirring was discontinued. The solid product was allowed to settle,and the supernatant liquid was siphoned off. A new amount of fresh TiCl₄was added to the flask, thereby reaching the initial liquid volume. Thetemperature was maintained at 110° C. for 0.5 hour. Again, the solid wasallowed to settle, and the liquid was siphoned off.

The solid was then washed three times with anhydrous hexane (250 mL ateach washing) at 60° C. and twice at 40° C.

500 mL of anhydrous heptane were added to the solid component and heatedunder stirring to 50° C. At the same temperature, under stirring, 10.5ml of THF were added dropwise. The temperature was then raised to 95°C., and the mixture was continuously stirred for 2 hours. Then, thetemperature was decreased to 80° C. The stirring was discontinued. Thesolid product was allowed to settle, and the supernatant liquid wassiphoned off.

The solid was washed twice with anhydrous hexane (2×250 mL) at 40° C.,recovered, dried under vacuum, and analyzed. The solid showed thefollowing characteristics: Ti=1.85% (by weight), Mg=14.6% (by weight),and tetrahydrofuran=32.6% (by weight).

General Procedure for the Preparation of the Solid Catalyst Componentfor Propylene Polymerization Test

Into a 500 ml round bottom flask, equipped with mechanical stirrer,cooler, and thermometer, 300 ml of TiCl₄ were introduced at roomtemperature under nitrogen atmosphere. After cooling to 0° C., whilestirring, 9,9-bis(methoxymethyl)fluorene and 9.0 g of themicrospheroidal adduct were sequentially added into the flask. Theamount of charged internal donor was such to have a Mg/donor molar ratioof 6. The temperature was raised to 100° C. and maintained for 2 hours.Thereafter, stirring was stopped. The solid product was allowed tosettle, and the supernatant liquid was siphoned off at 100° C. After thesupernatant was removed, additional fresh TiCl₄ was added, therebyreaching the initial liquid volume again. The mixture was then heated attemperature in the range of 110° C. and maintained at this temperaturefor 1 hour. Stirring was stopped again. The solid was allowed to settle,and the supernatant liquid was siphoned off. The solid was washed withanhydrous hexane six times in temperature gradient down to 60° C. andone time at room temperature. The resulting solid was then dried undervacuum and analyzed. The solid showed the following characteristics:Ti=4.1% (by weight), Mg=13.8% (by weight), and9,9-bis(methoxymethyl)fluorene=12.6% (by weight).

Example 1-3 and Comparative Examples 1-2 Preparation of Solid CatalystComponent A

A magnesium chloride and alcohol adduct containing about 3 mols ofalcohol was prepared following the method described in example 2 of U.S.Pat. No. 4,399,054, but working at 2000 RPM instead of 10000 RPM. Theadduct was subjected to a thermal treatment, under nitrogen stream, overa temperature range of 50-150° C. until a weight content of 24.4% ofalcohol was reached.

Into a 2 L four-necked round flask, purged with nitrogen, 1 L of TiCl₄was introduced at 0° C. Then, at the same temperature, 70 g of amicrospheroidal MgCl₂/EtOH adduct containing 24.4% wt of ethanol wereadded under stirring. The temperature was raised to 130° C. in 2 h andmaintained for 90 min. Then, the stirring was discontinued. The solidproduct was allowed to settle, and the supernatant liquid was siphonedoff. A new amount of fresh TiCl₄ was added to the flask, therebyreaching the initial liquid volume. The temperature was maintained at115° C. for 90 minutes. Again, the solid was allowed to settle, and theliquid was siphoned off. The solid was then washed three times withanhydrous iso-hexane (400 mL at each washing) at 60° C. and twice at 40°C.

At the end, the residual solid was suspended in 600 mL of dryiso-hexane. At the same temperature, under stirring, ethyl acetate wasadded dropwise to have a Mg/donor molar ratio of 1.7.

The temperature was raised to 50° C. The mixture was stirred for 2hours. Then, the stirring was discontinued. The solid product wasallowed to settle, and the supernatant liquid was siphoned off.

The solid was washed twice with anhydrous hexane (2×100 mL) at 40° C.,recovered, and dried under vacuum. The solid showed the followingcharacteristics: Ti=2.2% (by weight), Mg=15.3% (by weight), and ethylacetate=29.3% (by weight). The resulting solid catalyst components weretested in polymerization of ethylene for preparing HDPE. The results arelisted in Table 1.

Example 4 and Comparative Examples 3-4 Procedure for the Preparation ofthe Solid Catalyst Component (B)

A magnesium chloride and alcohol adduct containing about 3 mols ofalcohol was prepared following the method described in example 2 of U.S.Pat. No. 4,399,054, but working at 2000 RPM instead of 10000 RPM. Theadduct was subjected to a thermal treatment, under nitrogen stream, overa temperature range of 50-150° C. until a weight content of 25% ofalcohol was reached.

Into a 2 L four-necked round flask, purged with nitrogen, 1 L of TiCl4was introduced at 0° C. Then, at the same temperature, 70 g of amicrospheroidal MgCl₂/EtOH adduct containing 25% wt of ethanol wereadded under stirring. The temperature was raised to 140° C. in 2 h andmaintained for 120 minutes. Then, the stirring was discontinued. Thesolid product was allowed to settle, and the supernatant liquid wassiphoned off. The solid residue was then washed once with heptane at 80°C. and five times with hexane at 25° C. and dried under vacuum at 30° C.The solid showed the following characteristics: Ti=3.0% (by weight) andMg=8.7% (by weight). The resulting solid catalyst components were testedin polymerization of ethylene for preparing HDPE. The results are listedin Table 1.

TABLE 1 Al/ED Activity MIE MIP EX Catalyst ED m.r. Kg/g g/10′ g/10′ F/PF/E C1 A — 10.1 1.00 3.00 11.2 33.7 C2 A THF 15 9.8 0.94 2.73 9.1 26.5 1A DBU 15 8.0 0.44 1.24 8.5 23.9 2 A DBN 15 10.4 0.47 1.30 8.8 24.5 3 ADBU 30 9.7 0.68 2.0 8.8 25.7 C3 B — 21.5 0.16 0.66 13.6 56.3 C4 B THF 1013.4 0.11 0.43 12.3 48.2 4 B DBU 30 17.2 0.19 0.74 11.6 45.3

TABLE 2 ED Al/ED Activity MIE C₄ ⁻ XS Density EX type m.r. Kg/g/h g/10′% wt. % g/cm³ F/P F/E C5 THF 5 7.1 1.18 8.7 9.8 0.919 8.9 24.9 5 DBU 504.2 1.37 8.5 9.4 0.918 8.5 23.6

TABLE 3 ED Al/ED Activity XI MIL EX type m.r. Kg/g % g/10′ C6 none —82.7 94.5 30.0 6 TMG 20 38.9 98.5  8.40

What is claimed is:
 1. A catalyst for the polymerization of olefinscomprising: (a) a solid catalyst component containing Mg, Ti andoptionally an internal electron donor compound (ID), (b) an aluminumalky compound, and (c) an external electron donor (ED) of formula (I)

wherein the R¹ to R³ groups, equal to, or different from, each other,are selected from hydrogen or C₁-C₁₅ hydrocarbon groups, R group isselected from hydrogen, C₁-C₁₅ hydrocarbon groups, and —NR₂ groupswherein R groups have the same meaning as R¹ to R³ groups.
 2. Thecatalyst according to claim 1, wherein the solid catalyst component (a)contains at least one internal electron donor compound (ID) being amolecule containing at least one functional group selected from thegroup consisting gf esters, ethers, ketones, carbamates, carbonates,amines, amides, nitriles, alkoxysilanes, and mixtures thereof.
 3. Thecatalyst according to claim 1, wherein the ID compound is monofunctionalor multifunctional.
 4. The catalyst according to claim 3, wherein the IDcompound is multifunctional and contains two or more functional groupsselected from the group consisting of esters, ethers, ketones,carbamates, and carbonates.
 5. The catalyst according to claim 3,wherein the ID compound is monofunctional and contains a functionalgroup selected from the group consisting of C₁-C₈ alkyl esters ofaliphatic mono carboxylic acids and C₂-C₂₀ aliphatic ethers.
 6. Thecatalyst according to claim 1, wherein R¹ is selected from C₁-C₁₅hydrocarbon groups.
 7. The catalyst according to claim 1, wherein, inthe ED compound of formula (I), R¹ and R² are selected from C₁-C₁₀ alkylgroups, R³ is selected from hydrogen or C₁-C₅ alkyl groups, and R⁴ isselected from —NR₂ groups.
 8. The catalyst according to claim 1, whereinthe ED compound of formula (I) is tetra-methyl guanidine.
 9. Thecatalyst according to claim 4, wherein the solid catalyst component (a)comprises a difunctional ID compound.
 10. The catalyst according toclaim 1, wherein, in the ED compound of formula (I), the couples ofR1-R4 and R2-R3 are joined together to form non-aromatic ringstructures.
 11. The catalyst according to claim 10, wherein the ringstructures are made of five or more members.
 12. The catalyst accordingto claim 11, wherein the couple R¹-R⁴ forms a 5-7 members saturated ringstructure and the couple R²-R³ forms a six-member unsaturated ring,having a C═N double bond.
 13. The catalyst according to claim 1, whereinthe ED compound of formula (I) is selected from selected from the groupconsisting of 1.8-diazabicyclo[5.4.0]undec-7-ene (DBU) and1,5-diazabicyclo[4.3.0] non-5-ene (DBN).
 14. The catalyst according toclaim 5, wherein the solid catalyst component (a) comprises amonofunctional ID compound.
 15. A process for the homopolymerization orcopolymerization of olefins CH₂═CHR, wherein R is hydrogen or ahydrocarbyl radical with 1-12 carbon atoms, carried out in the presenceof a catalyst according to claim 1.